CN102504271B - Method for preparing hyperbranched polyester modified organic silicon resin - Google Patents
Method for preparing hyperbranched polyester modified organic silicon resin Download PDFInfo
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Abstract
The invention relates to organic silicon resin, in particular to a method for preparing hydroxyl-terminated hyperbranched polyester modified organic silicon resin. The method comprises the following steps of: adding 40 to 60 weight percent of hydroxyl-terminated hyperbranched polyester, 40 to 60 weight percent of organic silicon resin and a cross linking catalyst into a reactor; after heating the mixture for 1 to 3 hours at the temperature of 110 to 120 DEG C, warming to the temperature of 150 to 180 DEG C and heating for 1 to 3 hours; and finally, reducing the temperature to the room temperature and adding an organic solvent to regulate the solid content to the range of 60 to 70 percent so as to obtain the hydroxyl-terminated hyperbranched polyester modified organic silicon resin. The method combines the advantages of the hydroxyl-terminated hyperbranched polyester with the organic silicon resin and excellent heat resistance, low surface energy, excellent boiling resistance and excellent salt fog resistance are obtained. The resin prepared by the method disclosed by the invention can be used for preparing a coating with high temperature resistance and low surface energy.
Description
Technical field
The present invention relates to the organic high molecular compound field, relate to the macromolecular compound that only obtains with the silica reaction, be specifically related to silicone resin.
Background technology
Have in the silicone resin-the Si-O-Si-structure, demonstrate the performances such as good weathering resistance, thermotolerance, anti-stain characteristic and chemically stable.But pure silicone resin needs hot setting, and long construction inconvenience set time, and with the poor adhesive force of metallic substance, poor solvent resistance, physical strength are not high, and be expensive, so its use is subjected to restriction to a certain extent simultaneously.Other resins commonly used carry out modification to it.Vibrin has excellent metal adhesion, and the high good physical and mechanical properties of hardness and resistance to chemical corrosion preferably are used widely in coating industry.Use polyester modified organic silicon resin, can improve chemical resistance, mechanical property and the metal adhesion of silicone resin.Such as (Li Daming, the development of the durable coiled material finishing paint of organosilicon modified polyester type, coatings industries such as Li Daming, 2007,37 (12), 30-32) with hydroxyl polyester and silicone resin reaction preparation silicone resin modified poly ester, the modified poly ester of acquisition has good ageing resistance.Such as synthesis of hydroxy polyester modified organic silicon resins such as Yao Jiangliu, then be mixed with two component high-temperature resistant coatings with the aliphatic isocyanates solidifying agent.(Yao Jiangliu, Jia Chaoyang, the research of high performance organo-silicon modified hydroxyl telechelic polyester resin, Shanghai coating, 2007,45 (7), 4-6).But the hydroxyl polyester molecular weight that uses in the aforesaid method method is large, and hydroxy radical content is few, and viscosity is high, and the silicone resin reactive behavior is low, causes modified resin to exist silicone content few, and resistance toheat is poor, the anti-low shortcoming of performance of being infected with.
Hyperbranched polymer has highly branched structure and a large amount of end group active groups, has high resolution, low viscosity and higher chemical reactivity etc., is widely used in paint field.Low viscosity can reduce system viscosity with the blend of line polymer coating so that hyperbranched polymer is fit to be applied to high solid component coating, and the improvement system is mobile; High solvability can reduce the consumption of solvent, reduces cost, reduces noxious gas emission; Highly branched structure is difficult for crystallization so that the entanglement of hyperbranched polymer molecule interchain is less, makes coating have good film forming properties; Numerous terminal functionality can prepare and be fit to multi-purpose coating so that Hyperbranched Polymer has very strong correctability ability.Superbrnaching end-hydroxy polyester and silicone resin are reacted, can improve mechanical property, chemical resistance and the water resistance of silicone resin.But the performance of heat-resisting, the acidproof and salt spray resistance of existing silicone resin is still not ideal enough.
Summary of the invention
The technical problem that the present invention solves provides a kind of preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin, and the modified organic silicone resin of the method preparation has advantages of that heat-resisting low surface energy and acidproof salt spray resistance are good.
The scheme that the present invention solves above-mentioned technical problem is:
A kind of preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin, the method is comprised of following steps:
Silicone resin and the crosslinking catalyst of 40～60w% superbrnaching end-hydroxy polyester, 60～40w% are added in the reactor; After 1～3 hour, be warmed up to 150～180 ℃ 110～130 ℃ of lower heating, heated 1～3 hour; Be cooled at last room temperature, adding organic solvent adjustment solid content is 60～70%, wherein,
The weight-average molecular weight of described superbrnaching end-hydroxy polyester is 2000～4000, and be to be diprotic acid with diprotic acid and trivalent alcohol according to mol ratio: trivalent alcohol=1: 1～2 are carried out esterification and obtained; Wherein, described diprotic acid is a kind of or two or more in terephthalic acid, m-phthalic acid, hexanodioic acid and the Succinic Acid; Described trivalent alcohol is trimethylolethane, 1,3, and 5-benzene three is pure and mild 1,2, a kind of or two or more in the 4-benzene triol;
The weight-average molecular weight of described silicone resin is 800～2000, wherein contains 2.5～15% methoxy or ethoxy and 3～20% hydroxyl;
Described crosslinking catalyst consumption is superbrnaching end-hydroxy polyester weight 1～10%, is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, two octyloxy zinc and the two different octyloxy zinc;
Described organic solvent is one or more in butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate.
Silicone resin of the present invention can be by methltriethoxysilone, dimethyldiethoxysilane, the condensation reaction that is hydrolyzed of the siloxanes such as one phenyl triethoxy obtains, also can be by the monomethyl Trimethoxy silane, the condensation reaction that is hydrolyzed of dimethyldimethoxysil,ne, the siloxanes such as a phenyl trimethoxy obtains.
The siloxanes of the present invention condensation reaction that is hydrolyzed is the condensation reaction that is hydrolyzed of this area siloxanes commonly used, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Silicone resin of the present invention can also be KR9218, the company of SHIN-ETSU HANTOTAI of KR213, the company of SHIN-ETSU HANTOTAI of IC836, the company of SHIN-ETSU HANTOTAI of KR216, the Wa Ke company of KR214, the company of SHIN-ETSU HANTOTAI of KR212, the company of SHIN-ETSU HANTOTAI of KR211, the company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI KR217, Dow Corning Corporation 233, Dow Corning Corporation 249, the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3074, Dow Corning Corporation 3037 in a kind of or two or more.
Among the preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin of the present invention, the synthetic method of superbrnaching end-hydroxy polyester is that trivalent alcohol and diprotic acid esterification are obtained.Esterification process of the present invention is this area esterification process commonly used.Synthetic method of the present invention better is to contain following steps: add trivalent alcohol and diprotic acid in reactor; Per hour to heat up 20 ℃ rate of heating, be heated to 240 ℃, under 0.67～1.33kPa, be incubated 2～4h; Cool to room temperature.
Hyperbranched polyester modified organic silicon resin of the present invention, better technical scheme is: a kind of preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin, the method is comprised of following steps:
The silicone resin of 40～50w% superbrnaching end-hydroxy polyester, 50～60w% and the crosslinking catalyst of superbrnaching end-hydroxy polyester weight 1～5% are added in the reactor; After 1～3 hour, be warmed up to 150～180 ℃ 110～130 ℃ of lower heating, heated 1～3 hour; Adding at last organic solvent adjustment solid content is 60～70%;
Wherein silicone resin be KR9218, the company of SHIN-ETSU HANTOTAI of KR213, the company of SHIN-ETSU HANTOTAI of IC836, the company of SHIN-ETSU HANTOTAI of KR216, the Wa Ke company of KR214, the company of SHIN-ETSU HANTOTAI of KR212, the company of SHIN-ETSU HANTOTAI of KR211, the company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI KR217, Dow Corning Corporation 233, Dow Corning Corporation 249,3074 and Dow Corning Corporation of the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3037 in one or more kinds of mixtures.
Wherein crosslinking catalyst is a kind of or two or more in two octyloxy tin, two different octyloxy tin, two octyloxy zinc and the two different octyloxy zinc;
Wherein organic solvent is one or more in propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate;
Superbrnaching end-hydroxy polyester wherein, be to be diprotic acid with diprotic acid and trivalent alcohol according to mol ratio: trivalent alcohol=1: 1～1.4 are carried out esterification and are obtained;
Described diprotic acid is a kind of or two or more in terephthalic acid, m-phthalic acid and the hexanodioic acid;
Described trivalent alcohol is a kind of or mixture in trimethylolethane and 1,3, the 5-benzene triol.
The hyperbranched polyester modified organic silicon resin of method preparation of the present invention has the following advantages:
(1) hyperbranched polymer has highly branched structure, so that the entanglement of hyperbranched polymer molecule interchain is less, the hyperbranched polyester modified organic silicon resin of giving the present invention's preparation has low viscosity.
(2) superbrnaching end-hydroxy polyester contains abundant hydroxyl, can with silicone resin on alkoxyl group or silanol base generation crosslinking reaction, the hyperbranched polyester modified organic silicon resin of giving the method for the invention preparation has good acidproof and salt spray resistance.
The superbrnaching end-hydroxy polyester modified organic silicone resin that the method for the invention makes can be used for preparing high temperature resistant low surface energy coatings, and this coating has good water-fast and salt spray resistance.One of them ideal scheme is as follows:
A kind of high temperature resistant low surface energy coatings, this coating contain 60～80w% modified organic silicone resin, 10～20w% high-temperature resisting pigment filler and 5～20w% high boiling solvent, and wherein said modified organic silicone resin is prepared by the method for the invention.
High boiling solvent of the present invention refers to a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester, the methyl isoamyl ketone.
In the coating of the present invention, pigment is this area high-temperature resisting pigment commonly used, can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, also can be the organic high temperature-resistant pigment such as phthalocyanine blue.
In the coating of the present invention, filler is this area high temperature resistant filler commonly used, can be titanium dioxide, silicon-dioxide and silicon carbide.
Coating of the present invention can also contain the organosilicon auxiliary agent.
In the coating of the present invention, the organosilicon auxiliary agent is this area organosilicon auxiliary agent commonly used, plays the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive.Organosilicon auxiliary agent of the present invention can have silicone oil, organic silicon modified by polyether auxiliary agent etc.Organic silicon modified by polyether auxiliary agent of the present invention is this area organic silicon modified by polyether auxiliary agent commonly used, can be the CoatOSil series organic silicon modified by polyether auxiliary agent that steps figure new high-tech material company limited.
In the coating of the present invention, the consumption of organosilicon auxiliary agent is 1～5w%.
In the coating of the present invention, can also contain other auxiliary agents such as flow agent, viscosity modifier and dispersion agent.
The preparation method of coating of the present invention is this area preparation method commonly used, is about to superbrnaching end-hydroxy polyester modified organic silicone resin, pigment, filler, organosilicon auxiliary agent and high boiling solvent and is mixed to get.
The relative prior art of the present invention, have the following advantages: coating of the present invention with the superbrnaching end-hydroxy polyester modified organic silicone resin as base resin, superbrnaching end-hydroxy polyester and silicone resin carry out crosslinking reaction in this resin preparation process, the sticking power of superbrnaching end-hydroxy polyester is good, the advantage that water-fast and solvent nature is good and the low surface energy of silicone resin, excellent heat resistance, the advantages that water resistance is good is got up, and therefore coating of the present invention has the high heat resistance energy, good metal adhesion, low surface energy, excellent water boiling resistance and the advantage of salt spray resistance.
Embodiment
It below is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 96g (0.8mol); 1,3,5-benzene triol 25.2g (0.2mol);
Diprotic acid: terephthalic acid 132.8g (0.8mol); Succinic Acid 23.6g (0.2mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the 235g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3998.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 241mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form:
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 60g of step 1 preparation;
Silicone resin: the silicone resin KR216 40g of SHIN-ETSU HANTOTAI;
Two octyloxy tin: 1g.
B) preparation technology:
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 120 ℃ of insulations 2 hours; be warmed up to 160 ℃ of insulations 2 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 70%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 132g.
C) superbrnaching end-hydroxy polyester modified organic silicon performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
Resistance toheat: with test piece in 180 ℃ the baking 2h after, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, begin timing with furnace temperature to the requirement of experiment temperature, sample takes out through behind the continuous high temperature, be chilled to room temperature (25 ℃), observe the coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that namely coating heat resistance can be good.
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 100g of step 2 preparation;
Paint filler: carbon black 40g; Titanium dioxide 20g;
Organosilicon auxiliary agent: silicone oil
8g;
High boiling solvent: divalent ester mixture (DBE) 5g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
1* water boiling resistance performance: behind 180 ℃ of baking 2h, then cool to room temperature is positioned over test piece in 100 ℃ the distilled water with test piece, is heated to paint film and destroys, and occurs as bubbles loss of gloss, variable color, the phenomenons such as be full of cracks.
The 2* resistance toheat: with test piece in 180 ℃ the baking 2h after, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, begin timing with furnace temperature to the requirement of experiment temperature, sample takes out through behind the continuous high temperature, be chilled to room temperature (25 ℃), observe the coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that namely coating heat resistance can be good.
3* surface tension: under 25 ℃, measured by surface tension measuring instrument.
Embodiment 2:
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 168g (1.4mol); 1,2,4-benzene triol 37.8g (0.3mol); 1,3,5-benzene triol 37.8g (0.3mol);
Diprotic acid: m-phthalic acid 66.4g (0.4mol); Terephthalic acid 66.4g (0.4mol); Hexanodioic acid 29.2g (0.2mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2h; Cool off at last room temperature, obtain the 364g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 1990.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 638mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form:
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 40g of step 1 preparation;
Silicone resin: DOW CORNING 3037 60g;
Catalyzer: two octyloxy tin 3g.
B) preparation technology:
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 110 ℃ of insulations 3 hours; be warmed up to 180 ℃ of insulations 1 hour; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 160g.
C) superbrnaching end-hydroxy polyester modified organic silicon performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 160g of step 2 preparation;
Paint filler: carbon black 20g;
High boiling solvent: divalent ester mixture (DBE) 5g; Ethylene glycol ether acetate (CAC): 5g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 192g (1.6mol);
Diprotic acid: m-phthalic acid 157.7g (0.95mol); Hexanodioic acid 7.3g (0.05mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.78kPa, be incubated 2.5h; Cool off at last room temperature, obtain the 310g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 2611.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 507mgKOH/g.
2) silicone resin intermediate
A) form
Monomethyl Trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 18.7g (0.14mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 4.5mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone resin intermediate 290g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 10.6%; The methoxy content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 7.4%; R/Si=1.14; Ph/Me=1.04.
3) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 56g of step 1 preparation;
Silicone resin: the silicone resin 73.3g of the solid content 60% of step 2 preparation;
Catalyzer: two different octyloxy tin 2.7g.
B) preparation technology
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 115 ℃ of insulations 1.5 hours; be warmed up to 175 ℃ of insulations 1.5 hours; last cool to room temperature; adding dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate adjustment solid content is 65%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 141g.
C) superbrnaching end-hydroxy polyester modified organic silicon performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
4) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 100g of step 3 preparation;
Paint filler: phthalocyanine blue 20g; Silicon-dioxide 20g;
Organosilicon auxiliary agent: CoatOSil 7001 4g; Silicone oil
6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate (DBA) 5g; Ethylene glycol ether acetate (CAC) 5g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) be coated with performance
The performance index of coating
Embodiment 4:
1) superbrnaching end-hydroxy polyester
A) form:
Polyvalent alcohol: trimethylolethane 216g (1.8mol);
Diprotic acid: m-phthalic acid 166g (1.0mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.85kPa, be incubated 3.5h; Cool off at last room temperature, obtain the 340g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 2104.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 528mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 50g of step 1 preparation;
Silicone resin: the silicone resin KR211 23g of SHIN-ETSU HANTOTAI; The silicone resin KR214 27g of SHIN-ETSU HANTOTAI;
Catalyzer: two different octyloxy zinc 2g; Two octyloxy tin 1.5g.
B) preparation technology:
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 130 ℃ of insulations 1 hour; be warmed up to 155 ℃ of insulations 2.5 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate and butanols adjustment solid content is 70%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 125g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 120g of step 2 preparation;
Paint filler: silicon carbide 10g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; Silicone oil
4g;
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Divalent ester mixture (DBE) 10g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 5
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: 1,3,5-benzene triol 163.8g (1.3mol);
Diprotic acid: hexanodioic acid 29.2g (0.2mol); Terephthalic acid 132.8g (0.8mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2.5h; Cool off at last room temperature, obtain the 285g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3221.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 378mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form:
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 45g of step 1 preparation;
Silicone resin: silicone resin 233 35g of Dow Corning Corporation; Silicone resin 249 20g of Dow Corning Corporation;
Catalyzer: two octyloxy tin 3.5g.
B) preparation technology:
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 130 ℃ of insulations 1 hour; be warmed up to 170 ℃ of insulations 1 hour; last cool to room temperature; adding isopropylcarbinol and propylene glycol monomethyl ether adjustment solid content is 65%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 141g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 140g of step 2 preparation;
Paint filler: carbon black 20g; Silica 1 4g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; CoatOSil 7650 2g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 120g (1.0mol); 1,3,5-benzene triol 63g (0.5mol)
Diprotic acid: terephthalic acid 157.7g (0.95mol); Hexanodioic acid 7.3g (0.05mol);
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the 305g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 2947.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 463mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 45g of step 1 preparation;
Silicone resin: DOW CORNING silicone resin 3074 35g; The silicone resin KR212 20g of SHIN-ETSU HANTOTAI;
Catalyzer: two octyloxy tin 1g; Tetrabutyl titanate 1g.
B) preparation technology
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 125 ℃ of insulations 2 hours; be warmed up to 155 ℃ of insulations 2.5 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate and dipropylene glycol methyl ether adjustment solid content is 60%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 144g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 120g of step 2 preparation;
Paint filler: carbon black 20g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; CoatOSil 7510 2g; Silicone oil
4g;
High boiling solvent: divalent ester mixture (DBE) 12g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) superbrnaching end-hydroxy polyester
A) form
Trivalent alcohol: trimethylolethane 120g (1.0mol);
Diprotic acid: m-phthalic acid 141.1g (0.85mol); Succinic Acid 17.7g (0.15mol)
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.03kPa, be incubated 3.5h; Cool off at last room temperature, obtain the 234g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3982.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 247mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 58g of step 1 preparation;
Silicone resin: the silicone resin IC836 20g of Wa Ke company; The silicone resin Z-6108 10g of Dow Corning Corporation; The silicone resin KR213 12g of company of SHIN-ETSU HANTOTAI;
Catalyzer: tetrabutyl titanate 0.3g; Two octyloxy tin 0.2g.
B) preparation technology
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 130 ℃ of insulations 1 hour; be warmed up to 165 ℃ of insulations 2.5 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate and dipropylene glycol butyl ether adjustment solid content is 70%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 126g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 110g of step 2 preparation;
Paint filler: phthalocyanine blue 20g; Silicon-dioxide 5g; Titanium dioxide 5g;
High boiling solvent: divalent ester mixture (DBE) 40g; Isobutyl isobutyrate 20g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 144g (1.2mol)
Diprotic acid: m-phthalic acid 141.1g (0.85mol); Hexanodioic acid 21.9g (0.15mol)
B) synthesis step:
Heating is equipped with in trivalent alcohol, diprotic acid and hydroxycarboxylic acid adding, in the reactor of condensation and nitrogen protection, is warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the 366g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3663.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 252mgKOH/g.
2) silicone resin
A) form
Methltriethoxysilone: 69.1g (0.36mol)
Dimethyldiethoxysilane: 34.0g (0.21mol)
Phenyltriethoxysilane: 109.24g (0.43mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 5.5mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 42.7g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone resin intermediate 322g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 1808; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 20%; The oxyethyl group content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 2.5%; R/Si=1.21; Ph/Me=0.55.
3) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 56g of step 1 preparation;
Silicone resin: the silicone resin 73g that step 2 is synthetic
Catalyzer: two octyloxy zinc 2.5g; Two octyloxy tin 2g.
B) preparation technology
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 110 ℃ of insulations 3 hours; be warmed up to 170 ℃ of insulations 2 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 65%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 138g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
4) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 150g of step 2 preparation;
Paint filler: carbon black 10g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 3500 5g; Silicone oil
5g;
High boiling solvent: divalent ester mixture (DBE) 10g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) superbrnaching end-hydroxy polyester becomes
A) form
Trivalent alcohol: trimethylolethane 168g (1.4mol);
Diprotic acid: m-phthalic acid 157.7g (0.95mol); Succinic Acid 5.9g (0.05mol)
B) synthesis step
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the 290g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3055.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 428mgKOH/g.
2) silicone resin
A) form
Methltriethoxysilone: 44.5g (0.25mol)
Dimethyldiethoxysilane: 50.3g (0.34mol)
Phenyltriethoxysilane: 98.4g (0.41mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 7.0mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 43.1g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 80%, obtains silicone resin intermediate 230g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 1986; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 15%; The oxyethyl group content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 3%; R/Si=1.34; Ph/Me=0.44.
3) superbrnaching end-hydroxy polyester modified organic silicon
A) form
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 40g of step 1 preparation;
Silicone resin: the 60% solid content silicone resin 100g that step 2 is synthetic;
Catalyzer: two octyloxy tin 1g, two different octyloxy tin 0.6g.
B) preparation technology
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 125 ℃ of insulations 2 hours; be warmed up to 175 ℃ of insulations 1.52 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 148g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
4) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 150g of step 2 preparation;
Paint filler: phthalocyanine blue 20g; Titanium dioxide 20g;
Organic additive: CoatOSil 7510 8g;
High boiling solvent: divalent ester mixture (DBE) 2g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) superbrnaching end-hydroxy polyester
A) form:
Trivalent alcohol: trimethylolethane 132g (1.1mol);
Diprotic acid: terephthalic acid 149.4g (0.9mol); Hexanodioic acid 14.6g (0.1mol)
B) synthesis step:
Trivalent alcohol and diprotic acid adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2h; Cool off at last room temperature, obtain the 254g superbrnaching end-hydroxy polyester.
C) performance of superbrnaching end-hydroxy polyester
The weight-average molecular weight of superbrnaching end-hydroxy polyester adopts gel permeation chromatography to detect, and the result is 3887.
Hydroxyl value detects according to the described method of GB/T7193.2-1987, and the result is 292mgKOH/g.
2) superbrnaching end-hydroxy polyester modified organic silicon
A) form:
Superbrnaching end-hydroxy polyester: the superbrnaching end-hydroxy polyester 55g of step 1 preparation;
Silicone resin: the silicone resin KR9218 25g of SHIN-ETSU HANTOTAI; DOW CORNING silicone resin Z-6108 20g;
Catalyzer: two octyloxy zinc 0.6g; Two different octyloxy zinc 0.41g.
B) preparation technology:
Superbrnaching end-hydroxy polyester and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 120 ℃ of insulations 2 hours; be warmed up to 175 ℃ of insulations 2 hours; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 65%, obtains superbrnaching end-hydroxy polyester modified organic silicone resin 136g.
C) superbrnaching end-hydroxy polyester modified organic silicone resin performance
The over-all properties of superbrnaching end-hydroxy polyester modified organic silicon
3) coating
A) form
Superbrnaching end-hydroxy polyester modified organic silicone resin: the superbrnaching end-hydroxy polyester modified organic silicone resin 120g of step 2 preparation;
Paint filler: iron oxide red 30g; Titanium dioxide 20g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 7510:2g;
High boiling solvent: divalent ester mixture (DBE): 18g.
B) preparation technology
Paint filler, superbrnaching end-hydroxy polyester modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Claims (4)
1. the preparation method of a superbrnaching end-hydroxy polyester modified organic silicone resin, the method is comprised of following steps:
With the silicone resin of the superbrnaching end-hydroxy polyester of 40 ~ 60w%, 40 ~ 60w% and and crosslinking catalyst add in the reactor, after 1 ~ 3 hour, be warmed up to 150 ~ 180 ℃ 110 ~ 130 ℃ of lower heating, heated 1 ~ 3 hour, be cooled at last room temperature, adding organic solvent adjustment solid content is 60 ~ 70%; Wherein,
The weight-average molecular weight of described superbrnaching end-hydroxy polyester is 2000 ~ 4000, and it is to be that diprotic acid: trivalent alcohol=1:1 ~ 2 are carried out esterification and obtained by diprotic acid and trivalent alcohol according to mol ratio; Wherein, described diprotic acid is a kind of or two or more in terephthalic acid, m-phthalic acid, hexanodioic acid and the Succinic Acid; Described trivalent alcohol is trimethylolethane, 1,3, and 5-benzene three is pure and mild 1,2, a kind of or two or more in the 4-benzene triol;
The weight-average molecular weight of described silicone resin is 800 ~ 2000, wherein contains 2.5 ~ 15% methoxy or ethoxy and 3 ~ 20% hydroxyl;
Described crosslinking catalyst consumption is superbrnaching end-hydroxy polyester weight 1 ~ 10%, is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, two octyloxy zinc and the two different octyloxy zinc;
Described organic solvent is one or more in butanols, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate.
2. the preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin according to claim 1, it is characterized in that, the superbrnaching end-hydroxy polyester consumption is 40 ~ 50w%, and the silicone resin consumption is 50 ~ 60w%, and the crosslinking catalyst consumption is 1 ~ 5% of superbrnaching end-hydroxy polyester weight.
3. the preparation method of superbrnaching end-hydroxy polyester modified organic silicone resin according to claim 1 is characterized in that,
Described crosslinking catalyst is a kind of or two or more in two octyloxy tin, two different octyloxy tin, two octyloxy zinc and the two different octyloxy zinc;
Described organic solvent is one or more in propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate;
Described superbrnaching end-hydroxy polyester is to be that diprotic acid: trivalent alcohol=1:1 ~ 1.4 are carried out esterification and obtained with diprotic acid and trivalent alcohol according to mol ratio; Described diprotic acid is that terephthalic acid, m-phthalic acid and hexanodioic acid are wherein a kind of or two or more; Described trivalent alcohol is a kind of or mixture in trimethylolethane and 1,3, the 5-benzene triol.
4. high temperature resistant low surface energy coatings, this coating contains 60 ~ 80w% modified organic silicone resin, 10 ~ 20w% high-temperature resisting pigment filler and 5 ~ 20w% high boiling solvent; Wherein, described high boiling solvent is a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and the methyl isoamyl ketone, it is characterized in that, described modified organic silicone resin is made by the described method of one of claims 1 to 3.
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